CN103705965B - Making method of ultrathin antibiotic hydrogel film - Google Patents
Making method of ultrathin antibiotic hydrogel film Download PDFInfo
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Abstract
The invention discloses a making method of an ultrathin antibiotic hydrogel film. The making method comprises the following steps: mixing a component A with a buffering solution to obtain a copolymer solution I, and mixing a component B with the buffering solution to obtain a copolymer solution II; sequentially immersing a substrate in a concentrated sulfuric acid/hydrogen peroxide mixed solution and a silane coupling agent solution; and taking out the substrate, sequentially immersing the substrate in the copolymer solution I and the copolymer solution II, and repeating the immersion in the copolymer solution I and the copolymer solution II several times to obtain the ultrathin antibiotic hydrogel film. The component A is a polymer with the main chain containing a plurality of double bonds, and the component B is a polymer with the main chain containing a plurality of mercapto groups. The making method has the advantages of no need of a catalyst, rapid implementation under a physiologic condition, and good biocompatibility and maneuverability; and the made hydrogel film has the advantages of stable structure in a saline solution, accurate and controllable thickness, and free regulation of the thickness of the film in nanometer and micrometer scales, and has a good antibiosis effect on Escherichia coli and Staphylococcus aureus.
Description
Technical field
The present invention relates to the preparation of hydrogel thin film, be specifically related to a kind of preparation method of ultra-thin anti-bacterial hydrogel thin film.
Background technology
Conventional hydrogels is the colloid with high-hydroscopicity and swellability having macroscopic three dimensional network structure, formed with chemical bond or physical crosslinking effect.The mobility of its existing liquid and mobility have again the stability of solid.Because having good biocompatibility and multiple stimulating responsive, the fields such as hydrogel is fixed at enzyme, sensor, medicine controlled releasing, organizational project, water resource process are obtained for applies widely.And gel is prepared into the ultrathin membrane of nanometer grade thickness, then in the functionalization etc. of material surface, there are original innovative value and profound significance more.
In optics, biology, the field such as anticorrosion, control surface character manufactures the key with the new material of specific function.And surface functional layer can be prepared into nanoscale, both significant, challenging again.Common membrane material is prepared mainly through modes such as melting film forming and solution film formings, but is all difficult to regulate and control the thickness of nanoscale.In the last few years, along with appearance and the development of layer-by-layer, utilize electrostatic interaction, researcher assembles the thin film of multiple nanometer grade thickness in various substrate.Different according to component used, the character of the thin film formed is also varied.
Compared to traditional method, utilize layer-by-layer to prepare thin film and there is following advantage:
One, thickness can fine adjustment, as required, can be carried out the thickness of controlling diaphragm by the number of plies changing assembling;
Two, the thin film of nanoscale can be prepared, or even bilayer thin film;
Three, the formation of film can not limit by the geometry of substrate surface, and no matter whether surface is smooth, can form more uniform thin film on surface;
Four, simple to operate, with low cost.
Traditional layer-by-layer utilizes electrostatic interaction, and two of oppositely charged kinds of high molecular components are assembled.And the shortcoming easily occurring under severe conditions to destroy to overcome electrostatic assembly film expands its range of application simultaneously, layer-by-layer has obtained and has developed more far-reachingly.The driving force of assembling extend to hydrogen bond, DNA hybridization, host-guest interaction, metal-complexing effect and continuous chemical reaction etc. from electrostatic interaction.
" click chemistry " refers to the reaction of minority almost Perfect, synthesizes diversified compound by effective, modular approach, accelerates and optimizes course of reaction.It can carry out efficiently or even completely reacting under comparatively gentle condition; It has high selectivity, and byproduct of reaction is little.Therefore suitable attention and application is obtained in Polymer Synthesizing field.The important reaction of a class-" mercapto/alkene " reaction in " click chemistry " has especially without the need to catalyst, the powerful advantages that can rapidly and efficiently react under physiological status.Therefore " click chemistry " organically combines with layer-by-layer by we, is the method for a kind of innovation of the ultra-thin aquagel membrane of preparation.
Antibacterial is a large killer of harm publilc health, how effectively to control and prevent it to grow with spreading be a major challenge that society faces.And along with people are to improving constantly of requiring of quality of life, antimicrobial product is considered to one of tool new type health product with broad prospects for development.Research novel antibacterial material is significant to public health service.So-called " antibacterial ", refers to the process adopting chemistry or physical method kill bacteria or the breeding of obstruction bacterial growth and activity thereof, is sterilization and antibacterial general designation.Anti-biotic material generally can be divided into inorganic antiseptic, organic molecule antibacterial, natural molecule antibacterial and polymer antibacterial agent etc., wherein high-molecular anti-bacteria material can not infiltrate the advantages such as human body skin, zest is little, action effective is long because having, and enjoys the concern of researcher.According to the difference of antibacterial group, the high-molecular anti-bacteria material obtaining extensively research at present mainly contains quaternary ammonium salt, organic tin, halo amine, guanidine salt, chitosan class and derivant thereof etc.Wherein study comparatively extensive with polymeric quaternary ammonium salt anti-biotic material.Publication number is the bafta preparation method that the Chinese patent literature of CN102677453A discloses a kind of load organic quaternary ammonium salt and nano-titanium dioxide composite antibacterial agent, clean bafta is immersed dressing liquid; bath raio is 1:30 ~ 1:100; stir and drain; preliminary drying 10min ~ 60min at 80 DEG C; 105 DEG C ~ 120 DEG C bake 10min ~ 60min, cooling; The bafta of dipped dressing liquid is put into the distilled water wash 3 times that mass ratio is bafta 10 times, each persistent period 5min, then dry at 105 DEG C, cooling, obtains antibacterial cotton fabric; Publication number is that the Chinese patent literature of CN102040670A discloses a kind of preparation of carboxymethyl chitosan quaternary ammonium salt and the application in natural cosmetics antibacterial thereof, carboxymethyl chitosan is alkalized at Organic Alcohol, and then add quaternizing agent, be obtained by reacting that ammonium degree is 0.69 ~ 1.05, viscosity-average molecular weight is (0.92 ~ 2.36) × 104g/mol, degree of substitution by carboxymethyl is the carboxymethyl chitosan quaternary ammonium salt of 0.26 ~ 0.72.
High molecular quaternary not only has the basic characteristics of general high-molecular anti-bacteria material, also have that antibacterial pedigree is wide, structure is many, easy modification, can the feature of copolymerization, therefore the anti-biotic material of quaternary ammonium salt series is expected to play a significant role in multiple field.Such as, publication number is that the Chinese patent literature of CN102079713A discloses a kind of crosslinkable quaternary ammonium salt antibacterial monomer and preparation method thereof and the application at dental prosthetic material, solvent is added in tertiary amine species, and add halogenated hydrocarbons material and carry out back flow reaction, the product A obtained with toluene, benzene, dichloromethane or oxolane for solvent, add acyl chlorides and carry out back flow reaction, obtain quaternary ammonium salt B, then quaternary ammonium salt B is carried out purification; Another kind is for solvent with toluene, benzene, dichloromethane or oxolane, add acyl chlorides and tertiary amine species, adding triethylamine is auxiliary agent, the obtained tertiary amine containing C=C of reaction, tertiary amine with acetone, dichloromethane, acetonitrile for solvent, add halogenated hydrocarbons and carry out back flow reaction, then purification is carried out to quaternary ammonium salt monomer.Publication number is the method for sorting that the Chinese patent literature of CN101545203A discloses a kind of quaternary ammonium salt antibiotic textile based on sol-gel process, use sol-gel technique, take ammonium salt as catalyst, modified silicon dioxide sol is prepared by waterglass and quaternary ammonium salt or quaternary ammonium base cohydrolysis, employing is flooded, pad or pad the method for banking up forms antibacterial gel coating on fabric, thus give fabric stability lasting anti-microbial property, the antibiotic finish of textile can be widely used in.In a word, high molecular quaternary anti-biotic material has huge using value in fields such as antibacterial oral repair materials, sewage treating material, skincare material, composite and packaging material.
Summary of the invention
The object of the invention is the preparation method in order to expand two-dimentional hydrogel material and antibacterial surface material, provide a kind of with layer by layer " clicks " react and prepare the method for hydrogel thin film and the application in anti-biotic material thereof.This preparation method, without the need to catalyst, can be carried out fast in physiological conditions, have good biocompatibility and operability; The hydrogel thin film stability of preparation is surely strong, Stability Analysis of Structures in saline solution; Thickness controllable precise, thickness can carry out free regulation and control in nanometer and micro-meter scale; There is good antibacterial effect, have good antibacterial action to escherichia coli and staphylococcus aureus.
The invention discloses a kind of preparation method of ultra-thin anti-bacterial hydrogel thin film, comprise the steps:
(1) component A is dissolved in buffer solution, obtains copolymer solution I; B component is dissolved in buffer solution, obtains copolymer solution II;
(2) substrate is immersed in concentrated sulphuric acid/mixed solution of hydrogen peroxide carry out surface hydroxylation reaction, after taking-up, then immerse in silane coupler solution and carry out surperficial mercaptolation, after reaction terminates, substrate is taken out;
(3) substrate step (2) obtained is immersed in copolymer solution I, dries up after taking-up after deionized water wash; Immerse again in copolymer solution II, dry up after deionized water wash after taking-up;
(4) repeat step (3) several times, obtain described ultra-thin anti-bacterial hydrogel thin film;
Described component A is the polymer that main chain contains many double bonds, and described B component is the polymer that main chain contains many sulfydryls.
Utilize mercapto/alkene " click " to react, adopt two gel precursors that main chain contains many sulfydryls and many double bonds to react layer by layer.Mercapto/alkene " click " reaction is a kind of Michael addition reaction efficiently, when after substrate surface first grafting last layer sulfydryl, infiltrated in the copolymer solution I containing the component A of many double bonds, the partial double bond of component A and suprabasil sulfydryl generation additive reaction, thus surface has connected a layer component A molecule, it has again certain unreacted double bond group simultaneously, be impregnated in the copolymer solution II containing the B component of many sulfydryls again, again there is the additive reaction between sulfydryl and double bond, from and connected one deck B component, by that analogy, repeatedly circulate, the hydrogel thin film of any thickness can be obtained.
As preferably, described component A is Polyethylene Glycol-fumaryl chloride-alkyl double hydroxyethyl methyl halogenation amine copolymer thing, and the number-average molecular weight of copolymer is 5000 ~ 10000.Fumaryl chloride, as the source of double bond, is usually used in organic synthesis.
As preferably, described B component is Polyethylene Glycol-mercaptosuccinic acid. copolymer, and wherein mercaptosuccinic acid. is as the source of sulfydryl, and copolymer number-average molecular weight is 10000 ~ 15000.
Polyethylene Glycol is the polymer substance that the minority ratified by U.S. FDA can directly apply in human body, and it has good biocompatibility and water solublity, is one of optimum raw material preparing hydrogel material.As preferably, the molecular weight polyethylene glycol in described component A is 400 ~ 2000, and the molecular weight polyethylene glycol in B component is 400 ~ 2000.Based on the restriction of buying, described Polyethylene Glycol comprises PEG-400(molecular weight, lower same), PEG-600, PEG-1000 or PEG-2000.
As preferably, alkyl double hydroxyethyl methyl halogeno-amine in described component A is butyl double hydroxyethyl ammonio methacrylate, butyl double hydroxyethyl methyl bromide ammonium, hexyl double hydroxyethyl ammonio methacrylate, hexyl double hydroxyethyl methyl bromide ammonium, octyl group double hydroxyethyl ammonio methacrylate, octyl group double hydroxyethyl methyl bromide ammonium, decyl double hydroxyethyl ammonio methacrylate, decyl double hydroxyethyl methyl bromide ammonium, dodecyl double hydroxyethyl ammonio methacrylate, dodecyl double hydroxyethyl methyl bromide ammonium, myristyl double hydroxyethyl ammonio methacrylate, myristyl double hydroxyethyl methyl bromide ammonium, cetyl double hydroxyethyl ammonio methacrylate, cetyl double hydroxyethyl methyl bromide ammonium, octadecyl double hydroxyethyl ammonio methacrylate or octadecyl double hydroxyethyl methyl bromide ammonium.
Described buffer solution by sodium hydrogen phosphate and sodium dihydrogen phosphate formulated, buffer solution is neutral or alkalescence, and its pH value is 7.0 ~ 8.0.
As preferably, the mass percent concentration of described copolymer solution I is 0.1% ~ 5%, and the mass percent concentration of copolymer solution II is 0.1% ~ 5%.The concentration of copolymer solution is not particularly limited, but concentration is too low, greatly can reduce the preparation efficiency of hydrogel thin film; Excessive concentration, cost increases and post processing is complicated.
Described substrate, after the immersion of concentrated sulphuric acid/mixed solution of hydrogen peroxide, can carry out hydroxylating at substrate surface, provides active group for follow-up with the reaction of silane coupler.
The substrate object immersed in silane coupler solution is to modify sulfydryl at substrate surface, therefore, only needing in silane coupler with sulfydryl.As preferably, described silane coupler solution is (3-mercaptopropyi) trimethoxy silane/toluene solution, and concentration of volume percent is 0.5% ~ 5%.(3-mercaptopropyi) trimethoxy silane is reacted by the methoxyl group of himself and the hydroxyl of silicon chip surface, thus sulfydryl is grafted to silicon chip surface.
As preferably, 5 ~ 10min in copolymer solution I is immersed in the substrate described in step (3), immerses 5 ~ 10min in copolymer solution II.Often flood once, rear deionized water wash is taken out in substrate, then dries up with high pure nitrogen.
As preferably, described base material is Inorganic Non-metallic Materials, metal material or macromolecular material.Described Inorganic Non-metallic Materials can be silicon chip, piezoid or glass; Metal material can be titanium sheet or gold plaque; Macromolecular material can be polypropylene screen, polyethylene film, polyethylene terephthalate sheet material or polymethyl methacrylate sheet material.
The beneficial effect that the present invention compared with prior art has is as follows:
1) this preparation method is without the need to any catalyst, and can carry out fast in physiological conditions.There is good biocompatibility and operability; And be applicable to multiple substrate, not by the impact of substrate surface shape and roughness etc., there is the suitability widely.
2) the hydrogel thin film stability prepared of this method is strong, and in saline solution, structure is survivable; Thickness controllable precise, thickness can carry out free regulation and control at nanoscale and micro-meter scale.
3) hydrogel thin film that prepared by this method has good antibacterial effect, has good antibacterial action to escherichia coli and staphylococcus aureus.
Accompanying drawing illustrates:
Fig. 1 is the nuclear magnetic spectrogram of the Polyethylene Glycol-fumaryl chloride-dodecyl double hydroxyethyl ammonio methacrylate of preparation in embodiment 1;
Fig. 2 is the nuclear magnetic spectrogram of the Polyethylene Glycol-mercaptosuccinic acid. of preparation in embodiment 1;
Fig. 3 is the atomic force microscope height map of ultra-thin anti-bacterial hydrogel film prepared by embodiment 2;
Fig. 4 is that four kinds of anti-bacterial hydrogel thin film preparing respectively of comparative example and embodiment 1,2,3 are to colibacillary anti-bacteria test result;
Fig. 5 is that four kinds of anti-bacterial hydrogel thin film preparing respectively of comparative example and embodiment 1,2,3 are to the anti-bacteria test result of staphylococcus aureus;
The hydrogel thin film that in figure, a, b, c, d are corresponding in turn to comparative example, embodiment 1,2,3 prepares.
Detailed description of the invention
Below by embodiment, the present invention is further illustrated, and its object is only better to understand the present invention and unrestricted the scope of protection of the invention.
Embodiment 1
(1) preparation of component A
12mmol PEG-400,6mmol dodecyl double hydroxyethyl ammonio methacrylate is added in 250mL there-necked flask, dissolves with 70mL dichloromethane.Drip 20mmol fumaryl chloride and 36mmol triethylamine, at room temperature react 24 hours.The product obtained precipitates in cold diethyl ether, then through washing, dry, prepare Polyethylene Glycol-fumaryl chloride-dodecyl double hydroxyethyl ammonio methacrylate.Nuclear magnetic spectrogram is as shown in Figure 1 known, has prepared Polyethylene Glycol-fumaryl chloride-dodecyl double hydroxyethyl ammonio methacrylate by said method.
(2) preparation of copolymer solution I
The Na of configuration 50mM, pH=7.4
2hPO
4/ NaH
2pO
4buffer solution, is dissolved in 250mg Polyethylene Glycol-fumaryl chloride-dodecyl double hydroxyethyl ammonio methacrylate in 25ml buffer solution, obtains the copolymer solution I that concentration is 1%.
(3) preparation of B component
10mmol PEG-400 and 10mmol mercaptosuccinic acid. are added in there-necked flask, adds 0.02g trifluoromethanesulfonic acid scandium as catalyst, Depressor response 24h at 90 DEG C.Product, through extraction, oven dry, prepares Polyethylene Glycol-mercaptosuccinic acid..Nuclear magnetic spectrogram is as shown in Figure 2 known, has prepared PEG-400-mercaptosuccinic acid. by said method.
(4) preparation of copolymer solution II
250mg Polyethylene Glycol-mercaptosuccinic acid. is dissolved in 25ml buffer solution, obtains the copolymer solution II that concentration is 1%.
(5) preparation of ultra-thin anti-bacterial hydrogel film
Silicon chip is cut into 10mm × 10mm size, in concentrated sulphuric acid/30% hydrogen peroxide (volume ratio is 7:3) mixed solution, is heated to boiling, take out silicon chip deionized water rinsing, high pure nitrogen dries up.Silicon chip after process is placed in (3-mercaptopropyi) trimethoxy silane 1% toluene solution, reacts 1 hour.After taking-up, substrate is put into copolymer solution I, take out after dipping 5min, dry up with high pure nitrogen again after fully rinsing with deionized water; Again copolymer solution II is put in substrate, take out after dipping 5min, dry up with high pure nitrogen again after fully rinsing with deionized water; Once being designated as a circulation by often reacting in copolymer solution I and copolymer solution II, repeating 5 circulations, preparing ultra-thin anti-bacterial hydrogel film.
Fig. 3 is the AFM figure of ultra-thin anti-bacterial hydrogel film prepared by the present embodiment, clearly can see that the surface of film is rough form, meets the structure of gel by this figure; And the thickness that can obtain roughly film is about 100nm.
Comparative example
Adopt the experimental condition identical with step (5) in embodiment 1, but only substrate is used successively concentrated sulphuric acid/mixed solution of hydrogen peroxide, (3-mercaptopropyi) trimethoxy silane processes, clean and dry up, prepare hydrogel thin film.
Embodiment 2
Embodiment is identical with embodiment 1, is only that in step (5), substrate repeats 10 circulations in copolymer solution I and copolymer solution II.
Embodiment 3
Embodiment is identical with embodiment 1, is only that in step (5), substrate repeats 20 circulations in copolymer solution I and copolymer solution II.
Embodiment 4
Embodiment is identical with embodiment 2, is only that the kind of component A in step (1) is different, Polyethylene Glycol-fumaryl chloride-dodecyl double hydroxyethyl ammonio methacrylate is replaced with Polyethylene Glycol-fumaryl chloride-dodecyl double hydroxyethyl methyl bromide ammonium.
Embodiment 5
Embodiment is identical with embodiment 2, is only that the kind of component A in step (1) is different, Polyethylene Glycol-fumaryl chloride-dodecyl double hydroxyethyl ammonio methacrylate is replaced with Polyethylene Glycol-fumaryl chloride-cetyl double hydroxyethyl ammonio methacrylate.
Embodiment 6
Embodiment is identical with embodiment 2, is only that the kind of component A in step (1) is different, Polyethylene Glycol-fumaryl chloride-dodecyl double hydroxyethyl ammonio methacrylate is replaced with Polyethylene Glycol-fumaryl chloride-cetyl double hydroxyethyl methyl bromide ammonium.
Embodiment 7
Embodiment is identical with embodiment 2, is only that the kind of component A in step (1) is different, Polyethylene Glycol-fumaryl chloride-dodecyl double hydroxyethyl ammonio methacrylate is replaced with Polyethylene Glycol-fumaryl chloride-octadecyl double hydroxyethyl ammonio methacrylate.
Embodiment 8
Embodiment is identical with embodiment 2, is only that the kind of component A in step (1) is different, Polyethylene Glycol-fumaryl chloride-dodecyl double hydroxyethyl ammonio methacrylate is replaced with Polyethylene Glycol-fumaryl chloride-octadecyl double hydroxyethyl methyl bromide ammonium.
Embodiment 9
Embodiment is identical with embodiment 8, is only that the kind of component A in step (1) is different, the PEG-400 in Polyethylene Glycol-fumaryl chloride-octadecyl double hydroxyethyl methyl bromide ammonium is replaced with PEG-600.
Embodiment 10
Embodiment is identical with embodiment 8, is only that the kind of component A in step (1) is different, the PEG-400 in Polyethylene Glycol-fumaryl chloride-octadecyl double hydroxyethyl methyl bromide ammonium is replaced with PEG-1000.
Embodiment 11
Embodiment is identical with embodiment 8, is only that the kind of component A in step (1) is different, the PEG-400 in Polyethylene Glycol-fumaryl chloride-octadecyl double hydroxyethyl methyl bromide ammonium is replaced with PEG-2000.
Embodiment 12
Embodiment is identical with embodiment 2, is only that the kind of B component in step (3) is different, PEG-400 is replaced with PEG-600.
Embodiment 13
Embodiment is identical with embodiment 2, is only that the kind of B component in step (3) is different, PEG-400 is replaced with PEG-1000.
Embodiment 14
Embodiment is identical with embodiment 2, is only that the kind of B component in step (3) is different, PEG-400 is replaced with PEG-2000.
Embodiment 15
Embodiment is identical with embodiment 2, is only the dip time of substrate in copolymer I and copolymers II in step (5) is all adjusted to 8min.
Embodiment 16
Embodiment is identical with embodiment 2, is only the dip time of substrate in step 5 in copolymer I and copolymers II is all adjusted to 10min.
Embodiment 17
(1) ~ (4) are with step (1) ~ (4) in embodiment 2;
(5) piezoid is cut into 9mm × 30mm size, in concentrated sulphuric acid/hydrogen peroxide (volume ratio 7:3) mixed solution, is heated to boiling, take out silicon chip deionized water rinsing, high pure nitrogen dries up.Silicon chip after process is placed in γ-methacryloxypropyl trimethoxy silane 1% toluene solution, reacts 30 minutes.Substrate is put into copolymer solution I, take out after dipping 8min, dry up with high pure nitrogen again after fully rinsing with deionized water; Again copolymer solution II is put in substrate, take out after dipping 8min, dry up with high pure nitrogen again after fully rinsing with deionized water; Once being designated as a circulation by often reacting in copolymer solution I and copolymer solution II, repeating 10 circulations, preparing ultra-thin anti-bacterial hydrogel film.
Embodiment 18
Embodiment is identical with embodiment 17, is only the concentration of copolymer solution I in step (2) is brought up to 2%; In step (4), the concentration of copolymer solution II brings up to 2%.
Embodiment 19
Embodiment is identical with embodiment 17, is only the concentration of copolymer solution I in step (2) is brought up to 3%; In step (4), the concentration of copolymer solution II brings up to 3%.
Embodiment 20
Embodiment is identical with embodiment 17, is only the concentration of copolymer solution I in step (2) is brought up to 4%; In step (4), the concentration of copolymer solution II brings up to 4%.
Embodiment 21
Embodiment is identical with embodiment 17, is only the concentration of copolymer solution I in step (2) is brought up to 5%; In step (4), the concentration of copolymer solution II brings up to 5%.
Embodiment 22
(1) ~ (4) are with step (1) ~ (4) in embodiment 2;
(5) by polypropylene screen in oxygen barrier discharge environment, process 30 seconds, to introduce hydroxyl isopolarity group on surface.Polypropylene screen after process is placed in γ-methacryloxypropyl trimethoxy silane 1% toluene solution, processes 1 hour.Substrate is put into copolymer solution I, take out after dipping 8min, dry up with high pure nitrogen again after fully rinsing with deionized water; Again copolymer solution II is put in substrate, take out after dipping 8min, dry up with high pure nitrogen again after fully rinsing with deionized water; Once being designated as a circulation by often reacting in copolymer solution I and copolymer solution II, repeating 10 circulations, preparing ultra-thin anti-bacterial hydrogel film.
Embodiment 23
Embodiment is identical with embodiment 22, is only the polypropylene screen in step (5) is replaced with polyethylene film.
Embodiment 24
Embodiment is identical with embodiment 22, is only the polypropylene screen in step (5) is replaced with polyethylene terephthalate sheet.
Embodiment 25
Embodiment is identical with embodiment 22, is only the polypropylene screen in step (5) is replaced with polymethyl methacrylate thin slice.
Performance test
One, colibacillary antibacterial test
The ultra-thin anti-bacterial hydrogel thin film (b ~ d) of preparing respectively in the hydrogel thin film (a) prepared in comparative example and embodiment 1 ~ 3 is carried out colibacillary antibacterial test.Operational approach is as follows:
Solid medium is coated with a certain amount of escherichia coli or Escherichia coli bacteria liquid.One side silicon chip being loaded with hydrogel thin film is buckled in culture medium, then culture medium is upside down in 37 DEG C of incubators and cultivates 12 hours, after taking out, observe the size of silicon chip surrounding inhibition zone.
As shown in Figure 4, along with the increase of the gel number of plies, it is more obvious that inhibition zone size increases i.e. antibacterial effect gradually, which demonstrates the generation of reacting layer by layer; Illustrate that hydrogel prepared by the present invention possesses obvious anticolibacillary effect simultaneously.
Two, the antibacterial test of staphylococcus aureus
The ultra-thin anti-bacterial hydrogel thin film (b ~ d) of preparing respectively in the hydrogel thin film (a) prepared in comparative example and embodiment 1 ~ 3 is carried out the antibacterial test of staphylococcus aureus.Operational approach is as follows:
Solid medium is coated with a certain amount of staphylococcus aureus or staphylococcus aureus bacterium liquid.One side silicon chip being loaded with hydrogel thin film is buckled in culture medium, then culture medium is upside down in 37 DEG C of incubators and cultivates 12 hours, after taking out, observe the size of silicon chip surrounding inhibition zone.
As shown in Figure 5, along with the increase of the gel number of plies, it is more obvious that inhibition zone size increases i.e. antibacterial effect gradually, this demonstrates the generation of reacting layer by layer; Illustrate that hydrogel prepared by the present invention possesses significantly anti-staphylococcus aureus effect simultaneously.
Claims (7)
1. a preparation method for ultra-thin anti-bacterial hydrogel thin film, is characterized in that, comprise the steps:
(1) component A is dissolved in buffer solution, obtains copolymer solution I; B component is dissolved in buffer solution, obtains copolymer solution II;
(2) substrate is immersed in concentrated sulphuric acid/mixed solution of hydrogen peroxide carry out surface hydroxylation process, after taking-up, then immerse in silane coupler solution and carry out surperficial sulfhydrylation process, after reaction terminates, substrate is taken out;
(3) substrate step (2) obtained is immersed in copolymer solution I, dries up after taking-up after deionized water wash; Immerse again in copolymer solution II, dry up after deionized water wash after taking-up;
(4) repeat step (3) several times, obtain described ultra-thin anti-bacterial hydrogel thin film;
Described component A is Polyethylene Glycol-fumaryl chloride-alkyl double hydroxyethyl methyl halogenation amine copolymer thing, and described B component is Polyethylene Glycol-mercaptosuccinic acid. copolymer.
2. the preparation method of ultra-thin anti-bacterial hydrogel thin film according to claim 1, it is characterized in that, the molecular weight polyethylene glycol in described component A is 400 ~ 2000, and the molecular weight polyethylene glycol in B component is 400 ~ 2000.
3. the preparation method of ultra-thin anti-bacterial hydrogel thin film according to claim 1, it is characterized in that, alkyl double hydroxyethyl methyl halogeno-amine in described component A is butyl double hydroxyethyl ammonio methacrylate, butyl double hydroxyethyl methyl bromide ammonium, hexyl double hydroxyethyl ammonio methacrylate, hexyl double hydroxyethyl methyl bromide ammonium, octyl group double hydroxyethyl ammonio methacrylate, octyl group double hydroxyethyl methyl bromide ammonium, decyl double hydroxyethyl ammonio methacrylate, decyl double hydroxyethyl methyl bromide ammonium, dodecyl double hydroxyethyl ammonio methacrylate, dodecyl double hydroxyethyl methyl bromide ammonium, myristyl double hydroxyethyl ammonio methacrylate, myristyl double hydroxyethyl methyl bromide ammonium, cetyl double hydroxyethyl ammonio methacrylate, cetyl double hydroxyethyl methyl bromide ammonium, octadecyl double hydroxyethyl ammonio methacrylate or octadecyl double hydroxyethyl methyl bromide ammonium.
4. the preparation method of ultra-thin anti-bacterial hydrogel thin film according to claim 1, is characterized in that, the mass percent concentration of described copolymer solution I is 0.1% ~ 5%, and the mass percent concentration of copolymer solution II is 0.1% ~ 5%.
5. the preparation method of ultra-thin anti-bacterial hydrogel thin film according to claim 1, is characterized in that, described silane coupler solution is (3-mercaptopropyi) trimethoxy silane/toluene solution, and concentration of volume percent is 0.5% ~ 5%.
6. the preparation method of ultra-thin anti-bacterial hydrogel thin film according to claim 1, is characterized in that, 5 ~ 10min in copolymer solution I is immersed in the substrate described in step (3), immerses 5 ~ 10min in copolymer solution II.
7. the preparation method of ultra-thin anti-bacterial hydrogel thin film according to claim 1, is characterized in that, described base material is Inorganic Non-metallic Materials, metal material or macromolecular material.
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| US10743537B2 (en) * | 2017-12-12 | 2020-08-18 | International Business Machines Corporation | Monomer compositions with antimicrobial functionality |
| US10595527B2 (en) | 2017-12-12 | 2020-03-24 | International Business Machines Corporation | Antimicrobial polymers capable of supramolecular assembly |
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| CN1772797A (en) * | 2005-11-01 | 2006-05-17 | 浙江大学 | Covalent layer-by-layer self-assembling process for constructing polymer film on planar substrate |
| CN101905034A (en) * | 2010-07-19 | 2010-12-08 | 武汉理工大学 | Method for preparing biological polysaccharide self-assembly modificatory chitosan antibacterial biological material |
| CN102898661A (en) * | 2012-10-17 | 2013-01-30 | 浙江大学 | Polyethylene glycol hydrogel for orthotopic injection and preparation method thereof |
| US8496946B2 (en) * | 2011-03-10 | 2013-07-30 | International Business Machines Corporation | Antimicrobial hydrogels, methods of preparation thereof, and articles therefrom |
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| US20090098366A1 (en) * | 2007-09-07 | 2009-04-16 | Northwestern University | Methods of coating surfaces with nanoparticles and nanoparticle coated surfaces |
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| CN1772797A (en) * | 2005-11-01 | 2006-05-17 | 浙江大学 | Covalent layer-by-layer self-assembling process for constructing polymer film on planar substrate |
| CN101905034A (en) * | 2010-07-19 | 2010-12-08 | 武汉理工大学 | Method for preparing biological polysaccharide self-assembly modificatory chitosan antibacterial biological material |
| US8496946B2 (en) * | 2011-03-10 | 2013-07-30 | International Business Machines Corporation | Antimicrobial hydrogels, methods of preparation thereof, and articles therefrom |
| CN102898661A (en) * | 2012-10-17 | 2013-01-30 | 浙江大学 | Polyethylene glycol hydrogel for orthotopic injection and preparation method thereof |
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